Desulfurizing coke using a ferruginous material and a metal chloride

ABSTRACT

Coke is desulfurized at a temperature of at least 2,100*F., in the presence of a ferruginous material and a metal chloride. The ferruginous material and metal chloride may be blended with a coking feedstock, either solid or liquid, derived from coal or petroleum which is coked, with the desulfurization being effected during coking or subsequent thereto. Alternatively, the ferruginous material and metal chloride may be added to the coke which is then desulfurized at a temperature of at least 2,100*F. In the case of coke produced from pyrites containing coal, the ferruginous material can be omitted.

United States Patent 1 [111 3,873,427 Long et a1. Mar. 25, 1975 [541 DESULFURIZING COKE USING A 2,698,777 1/1955 Hartwick 201/17 GI S MATERIAL AND A METAL 2,824,047 2/1958 Gorin ct a1 201/20 CHLORIDE 3,768,988 10/1973 Meyers 201/17 [75] lnventors: Raymond 11. Long, Morristown;

Morgan C. Sze, Upper Montclair, Primary Examiner-A. Louis Monacell both of NJ. Assistant Examiner-David Edwards [73] Assigneez The Lummus Company Bloomfield, Attorney, Agent, or Firm-Mam & Jangaruthls [22] Filed: Aug. 31, 1973 [21] Appl. No.: 393,575 [57] ABSTRACT Rel ed Applic n Data Coke is desulfurized at a temperature of at least [63] Continuation-impart of Ser. No. 309,470, Nov, 24, 2,100F., in the presence ofa ferruginous material and 1972. abandoned. a metal chloride. The ferruginous material and metal chloride may be blended with a coking feedstock. eil l Cl 0, ther solid or liquid, derived from coal or petroleum 201/25, 423/461 which is coked, with the desulfurization being effected [51] Int. Cl C101) 57/06 during coking or subsequent thereto. Alternatively, [58] Field of Search 201/17, 20, 9, 25, 36, the ferruginous material and metal chloride may be 201/37, 19; 44/1 R; 423/461; 208/46, 106, added to the coke which is then desulfurized at a tem- 1. 223425, 2 perature of at least 2,100F. In the case of coke produced from pyrites containing coal, the ferruginous [56] References Cited material can be omitted.

UNITED STATES PATENTS 2.697118 10/1953 Phillips et a1. 201/19 18 Claims, 4 Drawing Figures Additive Water i Dissolver 1 Ground ferruginous Ground Material 71am? J r l I Dryer l L at Liquid carbonaceous Mixer Coker Feedstock L Petroleum Coker Distillaies Coke Caleination l Grinder 1 .1 1

Magnetic LFEBEQE'BJJ i Low Sulfur Low Sulfur Law Ash Coke Product Coke Product DESULFURIZING COKE USING A FERRUGINOUS MATERIAL AND A METAL CHLORIDE This application is a continuation-in-part of application Ser. No. 309,470 filed on Nov. 24, 1972 and now abandoned.

This invention relates to the desulfurization of coke, and more particularly to a new and improved process for producing a coke having a sulfur content of less than 0.85%.

There has been proposed a wide variety of processes for producing desulfurized coke. In general, however, such processes are not effective for producing a desulfurized coke from a wide variety of feedstocks having various sulfur contents, including sulfur contents of 4 percent and greater, which would meet todays standards of a sulfur content of less than 0.85 percent. and preferably less than 0.5 percent.

Accordingly, an object of the present invention is to provide a process for providing desulfurized coke.

Another object of the present invention isto provide a desulfurized coke having a sulfur content of less than 0.5%.

A further object of this present invention is to provide a process capable of producing a desulfurized coke having a sulfur content of less than 0.5% which is prepared from feedstocks having both high and low sulfur contents.

These and other objects of the present invention should be more readily apparent from reading the following detailed description thereof with reference to the accompanying drawings wherein:

FIGS. 14 are simplified schematic flow diagrams i1- lustrating various processing embodiments of the invention.

In accordance with the present invention, coke is desulfurized by heating thereof in the presence of a desulfurizing amount of desulfurizing additive. In the case where the coke is produced from a petroleum source, the desulfurizing additive is a ferruginous material (iron, oxide of iron or mixtures thereof) and at least one chloride salt which is either magnesium chloride, calcium chloride, ferrous chloride or ferric chloride. In the case where the coke is derived from coal containing iron in the form of pyrites, desulfurization can be effected with a desulfurizing amount of one or more of the aforementioned metal chloride salts, with improved desulfurization being obtained by the use of a ferruginous material in addition to the metal chloride salt. If the coal does not contain pyrites, i.e., pyrites is present in amounts less than 0.5% by weight of the coal, then both a ferruginous material and a chloride salt are used for effecting the desulfurization.

The coke, in admixture with the desulfurizing additive, is heated to a temperature of at least 2100F. for a time sufficient to produce a desulfurized coke having a sulfur content of no greater than 0.85%, and preferably no greater than 0.5%.

The coke which is desulfurized in accordance with the present invention may be a coke produced from any one of the wide variety of coking feedstocks including liquid and solid carbonaceous feedstocks, such as liquid petroleum stocks, liquid coking stocks derived furization at temperatures of at least 2100F. Alternatively, the desulfurizing additive may be added to the coke, and the coke subsequently desulfurized at temperatures of at least 2 1 00F. It is therefore to be understood that within the scope of the present invention the heating to effect desulfurization may be effected as part of the coking operation or subsequent to the coking operation, with the desulfurizing additive being combined with the coking feedstock prior to coking or combined with the coke from a coking operation.

The ferruginous material, as hereinabove noted, is either iron and/or an oxide of iron (ferrous oxide and- /or ferric oxide) and such ferruginous material may be employed in a impure state. Thus, for example, the ferruginous material may be added as taconite' fines, iron ore, iron etc. In general, the ferruginous material is employed in a finely divided state (e.g. a particle size of mesh with 50% or'more being 325 mesh) in an amount to provide a ferruginous material to coke weight ratio of from 1:4 to 1:30, and preferably from 1:10 to 1:16. In the case where the coke is produced from a coal containing pyrites in an amount of 0.5 weight percent or greater, it is possible to effect the required desulfurization without the use of a ferruginous material, i.e., the metal chloride salt is used as the only desulfurization additive; however, additional beneficial results are achieved by using the ferruginous additive in combination with the metal chloride salt; e.g., use of lower amounts of metal chloride salt, lower temperature, shorter periods for achieving the desired desulfurization and/or increased desulfurization. In some cases, even with the presence of pyrites, the ferruginous material may be required to achieve the desired degree of desulfurization.

The chloride salt (ferrous chloride and/or ferric chloride and/or calcium chloride and/or magnesium chloride) is generally employed in an amount to provide a chloride salt to ferruginous material weight ratio of from 4:1 to 1:100, and preferably a chloride salt to ferruginous material weight ratio of from 0.5:1 to 4:1 for ferrous and ferric chloride, and from 1:100 to 3:100 for the other chlorides. In the case where the chloride salt is used as the only desulfurizing additive (coke produced from coal containing pyrites), the chloride salt is employed in amounts to provide a chloride salt to coke weight ratio from about 0.0003 to 1 to about 1:1.

It is to be understood that the specific amounts of metal chloride salt and ferruginous material employed are coordinated to provide a desulfurizing amount of the combined additive.

The desulfurization is effected in a reducing atmosphere at a coke temperature of at least 2100F., with the temperature of the coke generally not exceeding 2600F. The desulfurization is preferably effected at a temperature from-2100F. to 2300F. (The furnace or oven in which the desulfurization is effected is generally at a temperature which is 100F. higher than the temperature of the coke). The coke is maintained at the desulfurization temperature for a time sufficient to reduce the sulfur content of the coke to no greater than 0.85%, and preferably no greater than 0.5%. The precise time required for such desulfurization will vary with the amount of sulfur originally present in the coke and the distribution, as to type, of the sulfur; i.e., pyritic, sulfate, sulfide, organic. In general, the time is at least one-half hour, with the time period generally not exceeding 16 hours.

Typically, the required desulfurization time is in the order of one to eight hours.

As hereinabove described, the desulfurizing additive may be admixed either with the feedstock which is to be converted to coke or with a previously produced coke. The chloride salt and ferruginous material are generally premixed either by dry blending of the ferruginous material and chloride salt both ground to the same fineness; spraying onto the ferruginous material an aqueous solution of thechloride salt, followed by drying; or pugging the ferruginous material with an aqueous solution of the chloride salt followed by drymg.

In the case where the coke is produced from a liquid feedstock derived from either a petroleum source, such as a petroleum crude residue, gilsonite, tar sand bitumen and the like, or a coal source, such as coal tar, coal tar pitch and the like, the mixture of ferruginous material and chloride salt is admixed with the liquid carbonaceous coker feedstock and the feedstock coked in a delayed coker or fluid coker as known in the art or in a carbonizer. The resulting coke, which includes the ferruginous material and chloride salt may then be desulfurized at the hereinabove described temperatures in conventional coke calcining equipment. The cooled coke from the calciner, containing no more than 0.85% sulfur, and preferably no more than 0.5% sulfur, may be used as a low sulfur fuel suitable for boilers. Alternatively, the product may be subjected to a magnetic separation technique to produce a lowsulfur, low ash fuel.

ln the case where a pyrite containing coal is to be employed as a coking feedstock, only the chloride salt need be added to the coal although improved results are obtained by the use of a ferruginous material. The chloride salt may be either dry mixed with the coal or the coal may be sprayed or pugged with an aqueous solution of the chloride salt. The coal may be either dried or admitted directly to thermal treatment. If the solid carbonaceous material does not include pyrites or the additional benefits derived from use of a ferruginous material are desired, then a mixture of ferruginous material and chloride salt, prepared as hereinabove described withreference to the liquid coker feedstocks, may be blended with the coal. Alternatively, a coal ferruginous material mixture may be dry blended with the chloride salt or the chloride salt added to such a mixture as an aqueous solution by either spraying or pugging.

The coal, including the ferruginous material and chloride salt, is then carbonized as known in the art. The carbonization of the solid carbonaceous feed includes thermal treatment at a temperature of at least 2l00F. for a time period sufficient to effect desulfurization. The specific process for producing coke from coal forms no part of the present invention and may be any one of the wide variety of processes employed in the art, provided that a portion of the overall carbonization process or subsequent thereto, includes thermal treatment at a temperature of at least 2100F. for a time sufficient to provide a coke containing no more than 0.85% sulfur, and preferably no more than 0.5% sulfur. Thus, for example, the coal may be carbonized in high temperature, slot-type coke ovens. Alternatively, the coal may be subjected to preheating and partial oxidation in a rabbled multiple-hearth furnace, followed by carbonization in one or more kiln-type carbonizers. As a further alternative, the coal may be ag-' glomerated, for example by briquetting, preheated and partially oxidized in a grate-kiln or rabbled unit and carbonized in a kiln, a grate kiln or a circular grate type unit.

In the case where the desulfurization is to be effected on a coke previously produced from a liquid or solid feedstock (derived from coal or petroleum), the ferruginous material and chloride salt may be added to the coke (in the case where sufficient pyrites is indigenous to the coke only chloride salt need be added), as hereinabove described. The ferruginous material may be either premixed with the chloride salt; eg, by dry blending or spraying or pugging the ferruginous material with an aqueous solution of the chloride salt, or the chloride salt may be dry blended with a mixture of ferruginous material and coke, or the chloride salt mixed with the coke as an aqueous solution by spraying or pugging. The coke, in admixture with the ferruginous material and chloride salt is then desulfurized, as hereinabove described.

The invention will be further described with respect to the drawings, but it is to be understood that the scope of the invention is not be limited thereby.

As shown in FIG. 1, the metal chloride additive is dissolved in water and wet-blended in a ball mill with the ground ferruginous material. Alternatively, the additive may be sprayed on the ferruginous material. In either case, the wet mixture is dried and then mixed with the liquid carbonaceous coker feedstock. As a further alternative, the metal chloride additive may be dry blended with the ferruginous material and subsequently added to the liquid carbonaceous feedstock, in which case the drier is by-passed.

While satisfactory results are obtained with particle size of 200 mesh with greater than 50 percent 325 mesh, it is advantageous to have the solids essentially percent 325 mesh, when it is fed to a conventional petroleum delayed or fluid coker facility.

Subsequent to coking, the coke is calcined in conventional equipment at temperatures and conditions set forth hereinabove. The cooled product is a low-sulfur fuel suitable for firing in boilers. Alternatively, it may be ground and magnetically separated to produce a low-sulfur, low-ash pulverized fuel.

In the embodiment illustrated in FIG. 2, a carbonizing kiln is substituted for the delayed or fluid coker. The metal chloride additive and ferruginous material are treated essentially as in FIG. 1, to the point of a dry mixture. In this case, effective results are attainable at 100 percent 1OO mesh and 50 percent 200 mesh for the solids. The solids are metered into an indirect-fired rotary-kiln type carbonizer where the liquid carbonaceous feed is sprayed to form balls of coke with the additives and ferruginous material uniformly dispersed therein. The carbonizer is maintained at a temperature in the range of 620750F. at the feed end and at 950l ,lOOF. at the discharge end. Any coke fines recovered in the calcination operation may be blended with the ferruginous material/additive mixture feed.

The coke balls discharged from the carbonizer are calcined in rotary kiln equipment at conditions as specified above to produce a low-sulfur coke product. As before, this may be ground and magnetically separated to produce a low sulfur, low-ash pulverized fuel.

The embodiments illustrated in FIG. 1 and FIG. 2 both contemplate mixing the additives with the fluid carbonaceous feedstock prior to coking or carbonizing.

However, it is also possible to carry out the invention with a high-sulfur, previously manufactured coke (or a coal). With this embodiment, which is shown in FIG. 3, it is possible for a fuel consumer to desulfurize purchased fuel prior to use.

As shown in FIG. 3, a petroleum coker is utilized in conventional fashion to produce coke. Additives may be dissolved in water and wet-blended with the ground ferruginous material, or the dissolved additive may be sprayed on the ferruginous material. The blend is then dried. Crushed petroleum coke is ground with this blend until all particles pass a 100 mesh screen and EXAMPLE I below those used in accordance with the present invention.

TABLE 1 CONTROL OF SULFUR CONTENT OF COKE Heating Rate: Elapsed Other Sulfur Time From Taconite Additives Level in 1500F. to Finishing Temp., Soaking Time at Addition, Wt. 7( Wt. 71 of Product Run T Hours T F. T,- Hours of Resid. Taconite Coke. 71

K-l 2.0 2200 1.0 None 4.6 K-?. 2.0 2200 2.0 17.3 2% MgCl 0.24 K-3 2.0 2200 1.0 17.3 3% MgCl 0.26 K 4 2.0 2200 2.0 15.0 2% CaCl 0.26/03 K-S 2.0 2200 1.0 None 3% MgC| 4.4 K-6 2.0 2200 1.0 9.0*** None 4.22 K-7 2.0 2000 16.0 5.0*** 3'71 MgCl 2.14 L-1 2.0 2200 16.0 3.0 330%FeCl 0.26/03 L-2 2.0 2200 16.0 6.0 250%FcCL, 0.29 L-3 2.0 2200 2.0 10.0 50/z'FcCl 026/028 L-4 2.0 2200 8.0 6.7** 180% FeCl 0.29 L-5 2.0 2200 1.0 3.3 380%FcCl 0.29 L-6 2.0 2200 2.0 10.0 125%FeC1 026/028 Taconite fines and iron filings were incorporated into the resid before coking. Chemical additives were added to the coke prior to heat treatment in the K series. and introduced into the rcsld prior to coking In the L series. Percentages shown are based on taconitc.

** lron filings (instead of tuconite) added. Wt. '71 on Coke.

preferably a 200 mesh screen. Alternatively, the petroleum coke may be dry-blended with the additive and ferruginous material. Calcination of this material'is carried out as partial combustion operation in a fluidized bed. Alternatively, the mixture may be granulated with water, dried, and calcined in a kiln-type unit. Temperature conditions of 2300F. are preferred, as before. As this material is finely ground to start with, it is in proper condition for use as a pulverized fuel without further treatment. Magnetic separation can be applied, if desired, to reduce the ash content.

FIG. 4, illustrates a processing sequence for producing desulfurized coke from coal. Coal is ground to 100 percent mesh, and if required, is intimately mixed with ground ferruginous or iron ore concentrate. The ground coal is then blended with an aqueous solution of metal chloride by either spraying or pugging and the mixture dried. Alternatively, the metal chloride may be added by dry blending.

The mixture of coal and metal chloride, which may further include added ferruginous material, is preheated and partially oxidized followed by carbonization, including desulfurization at a temperature of at least 2100F. The desulfurized coke is quenched and may be crushed and ground for use as a low sulfur fuel or sized for use as a low sulfur metallurgical coke.

The present invention will be further illustrated by the following examples, but it is to be understood that the scope of the invention is not be limited thereby. Unless otherwise indicated all parts and percentages are by weight.

EXAMPLE II An Illinois No. 6 coal (4.17% sulfur) is coked and desulfurized in accordance with the invention as .tabulated in Table 11.

In desulfurizing coke produced from coal in accordance with the present invention, it has been found that there is also obtained improved denitrification of the coal, i.e., the desulfurizing additive also functions to provide an accelerated rate of denitrification and/or reduced nitrogen contents. The following Example is illustrative of the denitrification results obtained in ac cordance with the desulfurization treatment of the present invention.

EXAMPLE 111 Illinois No. 6 coal (1.15% nitrogen) is coked and heated in the presence of a desulfurization additive in accordance with the invention and the denitrification 5 results are reported in Table 111:

The present invention is particularly advantageous in that a coke having a sulfur content of no greater than 0.85%, and preferably no greater than 0.5%, may be produced from a wide variety of feedstocks having a wide variety of sulfur contents including those having sulfur contents of 4 percent or greater.

The process of the present invention, depending on the initial sulfur content of the feedstock employed in producing the coke, is capable of providing greater than 90% desulfurization of feedstocks having sulfur contents of 4% and greater.

For fuel applications, the desulfurized coke from the above treatment may be burned directly as a pulverized fuel with the potential of satisfying anti-pollution requirements with no further precautions. Depending on the non-ferruginous additive employed, some benefit may derive from first washing the coke to remove any residual water soluble additives from the coke. If a lowash fuel is required, magnetic separation will effect the elimination of residual ferruginous materials.

When applied as a reductant where ferruginous values are indigenous to the process, this desulfurized coke, after particle size and temperature adjustment can be added directly to the pelletizers to adjust the integral carbon in the pellets to the level required for high or moderately high prereduction, permitting attainment of the desired sulfur levels in the finished pellets.

For possible use in carbon and graphite manufacture, wherein the ash content of the coke should be less than one percent,the coke after desulfurization is washed and magnetically separated to meet the necessary sulfur and ash requirements.

' Numerous modifications and variations of the present invention are possible in light of the above teachings and, therefore, within the scope of the appended claims, the invention may be described otherwise than as particularly described.

We claim: I

l. A process for desulfurizing coke, comprising:

heating coke in admixture with a desulfurizing amount of a desulfurizing additive toa temperature of at least 2100F, said desulfurizing additive comprising a ferruginous material selected from the group consisting of iron, oxides of iron and mixtures thereof and a metal chloride selected from the group consisting of magnesium chloride, calcium chloride, ferrous chloride, ferric chloride and mixtures thereof, and ferruginous material being present in a ferruginous material to coke weight ratio from 1:4 to 1:30 and the metal chloride being present in a metal chloride to ferruginous material weight ratio from 4:1 to 1:100; and

maintaining the coke at a temperature of at least 2100F to produce a desulfurized coke containing no more than 0.85 percent sulfur. 2. The process of claim 1 wherein the coke is a petroleum coke.

3. The process of claim 2 wherein the coke is maintained at a temperature of at least 2100F. to produce a coke having a sulfur content of no greater than 0.5 percent.

4. The process of claim 2 wherein the coke is heated to a temperature no greater than 2600F.

5. The process of claim 2 wherein the coke is heated to a temperature from 2100F. to 2300F.

6. The process of claim 2 wherein the desulfurizing additive is added to the petroleum feedstock prior to coking, the petroleum feedstock being coked and the coke being desulfurized in the presence of the desulfurizing additive.

7. The process of claim 2 wherein the coke is heated to atemperature of from 2100F. to 2300F.

8. The process of claim 3 wherein the ferruginous material which is admixed with the coke has a particle size of 'l00 mesh with at least 50 percent being -325 mesh,

9. A process for desulfurizing a coke produced from a pyrites containing coal, comprising:

heating said coke to a temperature of at least 2100F in admixture with a solid desulfurizing additive comprising a metal chloride selected from the group consisting of magnesium chloride, calcium chloride, ferrous chloride, ferric chloride and mixtures thereof, said metal chloride being present in a metal chloride to coke weight ratio from 0.000321 to 1:1; and

maintaining the coke at a temperature of at least 2100F to produce a desulfurized coke containing no more than 0.85 percent sulfur.

'10. The process of claim 9 wherein the desulfurizing additive further comprises a ferruginous material selected from the group consisting of an oxide of iron, iron and mixtures thereof, the ferruginous material being present in a ferruginous material to coke weight ratio from 1:4 to 1:30 and the metal chloride being present in a metal chloride to ferruginous material weight ratio of from 4:1 to 1:100.

11. The process of claim 9 wherein the coke is heated to a temperature no greater than 2600F.

12. The process of claim 9 wherein the coke is heated to a temperature from 2100F. to 2300F.

13. The process of claim 9 wherein the desulfurizing additive is added to the coal prior to coking thereof, the coal being coked and the coke being desulfurized in the presence of the desulfurizing additive.

14. The process of claim 10 wherein the coke is heated to a temperature from 2100F. to 2300F.

15. The process of claim 10 wherein the desulfurizing additive is added to the coal prior to coking thereof, the coal being coked and the coke being desulfurized in the presence of the desulfurizing additive.

16. The process of claim 10 wherein the coke is heated to a temperature of 2l00F. to 2300F.

17. The process of claim 10 wherein the coke is maintained at a temperature of at least 2100F to produce a coke having a sulfur content of no greater than 0.5 percent.

18. The process of claim 17 wherein the ferruginous material in admixture with the coke has a particle size of l00 mesh, with at least 50 percent being 325 mesh. 

1. A PROCESS FOR DESULFURIZING COKE, COMPRISING: HEATING COKE IN ADMIXTURE WITH A DESULFURIZING AMOUNT OF A DESULFURIZING ADDITIVE TO A TEMPERATURE OF AT LEAST 2100*F, SAID DESULFURIZING ADDITIVE COMPRISING A FERRUGINOUS MATERIAL SELECTED FROM THE GROUP CONSISTING OF IRON, OXIDES OF IRON AND MIXTURES THEREOF AND A METAL CHLORIDE SELECTED FROM THE GROUP CONSISTING OF MAGNESIUM CHLORIDE, CALCIUM CHLORIDE, FERROUS CHLORIDE, FERRIC CHLORIDE AND MIXTURES THEROF, AND FERRUGINOUS MATERIAL BEING PRESENT IN A FERRUGINOUS MATERIAL TO COKE WEIGHT RATIO FROM 1:4 TO 1:30 AND THE METAL CHLORIDE BEING PRESENT IN A METAL CHLORIDE TO FERRUGINOUS MATERIAL WEIGHT RATIO FROM 4:1 TO 1:100; AND MAINTAINING THE COKE AT A TEMPERATURE OF AT LEAST 2100*F TO PRODUCE A DESULFURIZED COKE CONTAINING NO MORE THAN 0.85 PERCENT SULFUR.
 2. The process of claim 1 wherein the coke is a petroleum coke.
 3. The process of claim 2 wherein the coke is maintained at a temperature of at least 2100*F. to produce a coke having a sulfur content of no greater than 0.5 percent.
 4. The process of claim 2 wherein the coke is heated to a temperature no greater than 2600*F.
 5. The process of claim 2 wherein the coke is heated to a temperature from 2100*F. to 2300*F.
 6. The process of claim 2 wherein the desulfurizing additive is added to the petroleum feedstock prior to coking, the petroleum feedstock being coked and the coke being desulfurized in the presence of the desulfurizing additive.
 7. The process of claim 2 wherein the coke is heated to a temperature of from 2100*F. to 2300*F.
 8. The process of claim 3 wherein the ferruginous material which is admixed with the coke has a particle size of -100 mesh with at least 50 percent being -325 mesh.
 9. A process for desulfurizing a coke produced from a pyrites containing coal, comprising: heating said coke to a temperature of at least 2100*F in admixture with a solid desulfurizing additive comprising a metal chloride selected from the group consisting of magnesium chloride, calcium chloride, ferrous chloride, ferric chloride and mixtures thereof, said metal chloride being present in a metal chloride to coke weight ratio from 0.0003:1 to 1:1; and maintaining the coke at a temperature of at least 2100*F to produce a desulfurized coke containing no more than 0.85 percent sulfur.
 10. The process of claim 9 wherein the desulfurizing additive further comprises a ferruginous material selected from the group consisting of an oxide of iron, iron and mixtures thereof, the ferruginous material being present in a ferruginous material to coke weight ratio from 1:4 to 1:30 and the metal chloride being present in a metal chloride to ferruginous material weight ratio of from 4:1 to 1:100.
 11. The process of claim 9 wherein the coke is heated to a temperature no greater than 2600*F.
 12. The process of claim 9 wherein the coke is heated to a temperature from 2100*F. to 2300*F.
 13. The process of claim 9 wherein the desulfurizing additive is added to the coal prior to coking thereof, the coal being coked and the coke being desulfurized in the presence of the desulfurizing additive.
 14. The process of claim 10 wherein the coke is heated to a temperature from 2100*F. to 2300*F.
 15. The process of claim 10 wherein the desulfurizing additive is added to the coal prior to coking thereof, the coal being coked and the coke being desulfurized in the presence of the desulfurizing additive.
 16. The process of claim 10 wherein the coke is heated to a temperature of 2100*F. to 2300*F.
 17. The process of claim 10 wherein the coke is maintained at a temperature of at least 2100*F to produce a coke having a sulfur content of no greater than 0.5 percent.
 18. The process of claim 17 wherein the ferruginous material in admixture with the coke has a particle size of -100 mesh, with at least 50 percent being -325 mesh. 